Specific interactions generate stability of the component parts in blends. Present work aims to elucidate intermolecular interactions in polystyrene/novolac blends by means of Infrared spectroscopic studies. It was found that strong interactions were observed at band 3095 cm-1 assigned to aromatic C-H stretching vibrations, at band 2980 cm-1 assigned to aliphatic C-H stretching vibration and at band 1635 cm-1 assigned to C=C stretch vibration of aromatic ring system. Maximum interaction was observed in blend consisting polystyrene/novolac (80:20 by parts, in this study it is blend B). Mechanical and thermal properties of the blends were also studied. Tensile strength data was found maximum in blend B. Nonisothermal method of Freeman and Carrol was used to investigate the kinetics of thermal degradation. The reactions were studied by thermogravimetry in nitrogen atmosphere. Decomposition of the blends was found in consecutive stages. The activation energies were determined for each stage of reactions. From thermal studies, blend B was found to be most stable. A degradation mechanism was suggested by compiling the reports of previous authors. © 2006 Wiley Periodicals, Inc.